WO2018196362A1 - Réacteur à lit fluidisé et procédé de production d'oléfine à faible teneur en carbone co-produite par para-xylène à partir de benzène et de méthanol et/ou d'éther diméthylique - Google Patents

Réacteur à lit fluidisé et procédé de production d'oléfine à faible teneur en carbone co-produite par para-xylène à partir de benzène et de méthanol et/ou d'éther diméthylique Download PDF

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WO2018196362A1
WO2018196362A1 PCT/CN2017/112812 CN2017112812W WO2018196362A1 WO 2018196362 A1 WO2018196362 A1 WO 2018196362A1 CN 2017112812 W CN2017112812 W CN 2017112812W WO 2018196362 A1 WO2018196362 A1 WO 2018196362A1
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Prior art keywords
fluidized bed
distributor
methanol
gas
bed reactor
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PCT/CN2017/112812
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English (en)
Chinese (zh)
Inventor
叶茂
张涛
张今令
刘中民
贾金明
唐海龙
何长青
王贤高
张骋
李华
赵银峰
李承功
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中国科学院大连化学物理研究所
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Priority to SG11201910011U priority Critical patent/SG11201910011UA/en
Priority to KR1020197034519A priority patent/KR102325164B1/ko
Priority to EP17907100.6A priority patent/EP3617177A4/fr
Priority to RU2019133740A priority patent/RU2745438C1/ru
Priority to JP2019555175A priority patent/JP7035077B2/ja
Priority to US16/608,444 priority patent/US11072571B2/en
Publication of WO2018196362A1 publication Critical patent/WO2018196362A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/004—Sparger-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/88—Growth and elimination reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00752—Feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00911—Sparger-type feeding elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • Paraxylene is one of the basic organic raw materials in the petrochemical industry. It has a wide range of applications in chemical fiber, synthetic resins, pesticides, pharmaceuticals, and polymer materials.
  • p-xylene production mainly uses toluene, C 9 aromatic hydrocarbons and mixed xylene as raw materials, and is obtained by disproportionation, isomerization, adsorption separation or cryogenic separation. Since the p-xylene content in the product is controlled by thermodynamic equilibrium, p-xylene only accounts for ⁇ 24% of the C 8 mixed aromatics, and the material circulation processing amount is large during the process, and the equipment is large and the operation cost is high.
  • Methanol is both a raw material for the alkylation of benzene and/or toluene and methanol, and is also a raw material for the MTO reaction, but the MTO reaction rate is much higher than the alkylation reaction rate of benzene and/or toluene and methanol.
  • Our experimental studies have shown that when benzene and methanol are co-fed and the methanol content of the feedstock is low, the MTO reaction quickly consumes most of the methanol (alkylation reactant) and inhibits the alkylation of benzene and/or toluene and methanol. The reaction yield is low in p-xylene.
  • the intake ring pipe is connected to the intake pipe air path, and the intake ring pipe is arranged on a plane perpendicular to a flow direction of the gas of the first distributor;
  • a process for the co-production of a light olefin with benzene and methanol and/or dimethyl ether to produce para-xylene Through different raw material streams distributed in different areas to achieve mass transfer control, and then coordinate and optimize the co-feed system to improve the reaction yield.
  • the alkylation of benzene and methanol produces a p-xylene reaction in which the reaction rates of the alkylation reaction and the MTO reaction are greatly different, and the MTO reaction inhibits the alkylation reaction, and thus the conversion of benzene is low.
  • the fluidized bed reactor provided by the present application coordinates and optimizes the competition of the alkylation reaction and the MTO reaction through mass transfer control, thereby improving the conversion of benzene and the yield of p-xylene.
  • stream C comprising para-xylene and a lower olefin.
  • the stream C enters the settling zone and the gas-solids separator, and the stream C is separated to obtain low-carbon olefins, p-xylene, chain hydrocarbon by-products, aromatic by-products and unconverted benzene, unconverted methanol and/or Methyl ether
  • methanol and/or dimethyl ether means that the methanol in the feed may be replaced in whole or in part by dimethyl ether, including three cases: only methanol; or only dimethyl ether; or methanol and two. Methyl ether has it.
  • methanol and/or dimethyl ether and benzene includes three cases: methanol and benzene; or dimethyl ether and benzene; or methanol, dimethyl ether and benzene.
  • the sum of the mass percentages of methanol and dimethyl ether in the stream A is from 0% to 30%. That is, the stream A entering the first distributor does not contain methanol, or the mass percentage of methanol in the stream A entering from the first distributor does not exceed 30%.
  • the sum of the mass percentages of methanol and dimethyl ether in the stream A is from 2% to 20%.
  • the regenerator has a gas phase linear velocity of 0.2 m/s to 2 m/s and a regeneration temperature of 500 to 800 °C.
  • the present invention coordinates and optimizes the competition between the alkylation reaction and the MTO reaction by controlling the concentration of methanol and/or dimethyl ether relative to benzene to increase the yield of p-xylene and Low-carbon olefin selectivity to ensure that neither the MTO reaction rapidly consumes most of the methanol and/or dimethyl ether to inhibit the alkylation reaction, nor does it occur due to the high levels of methanol and/or dimethyl ether.
  • MTO reaction occurs in a large amount, and the amount of benzene adsorbed in the catalyst per unit time is low, which is disadvantageous for the alkylation reaction.
  • FIG. 1 is a schematic view showing the structure of a fluidized bed reactor in an embodiment of the present application.
  • 1-first gas distributor 2-second gas distributor, 3-reaction zone, 4-settling zone, 5-gas-solids separator, 6-stripping zone, 7-regenerated catalyst delivery pipe.
  • FIGS. 1 and 2 a fluidized bed reactor in which benzene and methanol produce p-xylene co-produced lower olefins is shown in FIGS. 1 and 2, and includes a first gas distributor 1 and a second gas distributor 2 , reaction zone 3, settling zone 4, gas-solids separator 5, stripping zone 6 and regenerated catalyst delivery pipe 7.
  • the first gas distributor 1 may be a dendritic gas distributor.
  • the second gas distributor 2 is a microporous gas distributor.
  • the side and end faces of the microporous core tube 2-3 have a uniform microporous structure, the pore diameter of the micropores is 0.5 ⁇ m to 50 ⁇ m, the porosity is 25-50%, and the gas velocity in the tube is 0.1 m/s to 10 m/ s.
  • the gas velocity in the tube is from 1 m/s to 10 m/s.
  • the concentration of methanol and/or dimethyl ether decreases rapidly and approaches zero along the axial direction of the reactor, from upstream to downstream, while the concentration of benzene Slowly decreasing, in the upstream region of the reactor, the alkylation rate is limited by the mass transfer rate of benzene in the catalyst pores, and in the downstream region of the reactor, with the rapid consumption of methanol and the diffusion of methanol With rapid reduction, the alkylation rate is limited by the mass transfer rate of methanol in the catalyst channels. Maintaining a relatively stable methanol concentration in the reactor is one of the effective ways to promote alkylation.
  • the first gas distributor 1 belongs to a two-dimensional gas distributor, that is, the material gas is relatively uniformly distributed in the plane of the first gas distributor 1.
  • a portion of the methanol and/or dimethyl ether is introduced by the first gas distributor 1 and another portion of the methanol and/or dimethyl ether is introduced by the second gas distributor 2, which is densely packed in the microporous core.
  • the micropores on the tube 2-3 are distributed to the reaction zone 3 around the micropore core tube 2-3. Therefore, in the region where the second gas distributor 2 is located, the methanol concentration is substantially stabilized, and only in the downstream region of the reaction zone 3, the methanol concentration rapidly decreases.
  • the concentration of methanol in the region where the second gas distributor 2 is located can greatly increase the alkylation reaction rate of benzene and/or toluene.
  • a method for producing a para-xylene co-production of a lower olefin comprises the following steps:
  • the fluidized bed reactor comprising a first gas distributor 1, a second gas distributor 2, a reaction zone 3, a settling zone 4, a gas-solid separator 5, a stripping zone 6 and a regenerated catalyst delivery pipe 7, a first gas distributor 1 placed at the bottom of the reaction zone 3, a second gas distributor 2 placed in the reaction zone 3, and a settling zone 4 in reaction Above the zone 3, a gas-solid separator 5 is disposed in the settling zone 4, a product outlet is provided at the top, a stripping zone 6 is below the reaction zone 3, and an upper portion of the reaction zone 3 is connected to the regenerated catalyst delivery pipe 7.
  • Stream A Benzene, aromatic by-products and methanol mixtures.
  • Stream A is passed from the first gas distributor 1 to the reaction zone 3 of the fluidized bed reactor, and the mass of methanol in the mixture of stream A is 4%.
  • the stream B enters the reaction zone 3 of the fluidized bed reactor from the second gas distributor 2, and the mass ratio of the methanol entering from the second gas distributor 2 to the methanol entering the first gas distributor 1 is 9:1;
  • the gas phase linear velocity of the bed reactor is from 0.8 m/s to 1.0 m/s, and the temperature is 450 ° C.
  • the reactants in the reaction zone 3 are contacted with the catalyst to form a gas phase stream comprising para-xylene and a lower olefin.
  • the gas phase stream enters the settling zone 4, the gas-solid separator 5, via the product outlet Enter the subsequent separation section.
  • the first gas distributor 1 is a dendritic gas distributor and the second gas distributor 2 is a microporous gas distributor.
  • Stream A a mixture of benzene, aromatic by-products and dimethyl ether.
  • Stream A is passed from the first gas distributor 1 to the reaction zone 3 of the fluidized bed reactor, and the mixture of stream A has a mass content of 10% of dimethyl ether.
  • Stream B enters reaction zone 3 of the fluidized bed reactor from second gas distributor 2, and the mass ratio of methanol entering from second gas distributor 2 to methanol entering from first gas distributor 1 is 19:1.
  • the gas phase linear velocity of the fluidized bed reactor is from 1.3 m/s to 1.5 m/s, and the temperature At 500 ° C, the reactants in the reaction zone 3 are contacted with the catalyst to form a gas phase stream comprising para-xylene and a low-carbon olefin; the gas phase stream enters the settling zone 4, the gas-solid separator 5, and enters a subsequent separation section via the product outlet;
  • the catalyst forms a catalyst to be produced after carbon deposition in the reaction zone, and the catalyst to be produced is subjected to stripping and regenerated into a fluidized bed regenerator.
  • the gas phase linear velocity of the fluidized bed regenerator is 1.5 m/s, and the temperature is 600 ° C.
  • the catalyst enters the fluidized bed reactor via the regenerated catalyst delivery line 7.
  • the temperature is 550 ° C
  • the reactants in the reaction zone 3 and the catalyst contact, to form a gas phase stream C containing para-xylene and low-carbon olefin
  • the gas phase stream enters the settling zone 4, the gas-solid separator 5, via
  • the product outlet enters a subsequent separation section
  • the catalyst forms a catalyst to be produced after carbon deposition in the reaction zone, and the catalyst to be produced is stripped and regenerated into a fluidized bed regenerator, and the gas phase linear velocity of the fluidized bed regenerator is 1.0 m/s.
  • the regenerated catalyst enters the fluidized bed reactor via the regenerated catalyst delivery pipe 7.
  • the fluidized bed reactor comprising a first gas distributor 1, a second gas distributor 2, a reaction zone 3, a settling zone 4, a gas-solid separator 5, a stripping zone 6 and a regenerated catalyst delivery pipe 7, a first gas distributor 1 placed at the bottom of the reaction zone 3, a second gas distributor 2 placed in the reaction zone 3, and a settling zone 4 in reaction Above the zone 3, a gas-solid separator 5 is disposed in the settling zone 4, a product outlet is provided at the top, a stripping zone 6 is below the reaction zone 3, and a bottom of the reaction zone 3 is connected to the regenerated catalyst delivery pipe 7.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un réacteur à lit fluidisé pour la production d'oléfine à faible teneur en carbone co-produite par du para-xylène à partir de benzène et de méthanol et/ou d'éther diméthylique, comprenant un premier distributeur et un second distributeur. Le premier distributeur est situé sur le fond du lit fluidisé, et le second distributeur est situé en aval du premier distributeur le long d'une direction d'écoulement de gaz. L'invention concerne un procédé de production d'une oléfine à faible teneur en carbone co-produite par du para-xylène, comprenant principalement les étapes suivantes consistant à : (1) amener un fluide A à entrer dans une zone de réaction du réacteur à lit fluidisé à partir du premier distributeur de gaz ; (2) amener un fluide B à entrer dans la zone de réaction du réacteur à lit fluidisé à partir du second distributeur de gaz ; (3) amener un réactif à entrer en contact avec un catalyseur dans la zone de réaction pour générer un flux d'objet en phase gazeuse comprenant du para-xylène et une oléfine à faible teneur en carbone. La présente invention coordonne et optimise la concurrence entre une réaction d'alkylation de benzène et une réaction MTO par contrôle du transfert de masse afin de faciliter l'effet synergique entre les deux réactions, de façon à augmenter de manière considérable le taux de conversion de benzène et le rendement de para-xylène.
PCT/CN2017/112812 2017-04-27 2017-11-24 Réacteur à lit fluidisé et procédé de production d'oléfine à faible teneur en carbone co-produite par para-xylène à partir de benzène et de méthanol et/ou d'éther diméthylique WO2018196362A1 (fr)

Priority Applications (6)

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SG11201910011U SG11201910011UA (en) 2017-04-27 2017-11-24 Fluidized bed reactor and method for producing para-xylene and co-producing light olefins from benzene and methanol and/or dimethyl ether
KR1020197034519A KR102325164B1 (ko) 2017-04-27 2017-11-24 벤젠과 메탄올 및/또는 디메틸에테르에 의한 파라자일렌의 제조 및 저탄소 올레핀의 동시 제조를 위한 유동상 반응기 및 제조 방법
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RU2019133740A RU2745438C1 (ru) 2017-04-27 2017-11-24 Реактор с кипящим слоем и способ получения пара-ксилола и совместного получения низших олефинов из бензола и метанола и/или диметилового эфира
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110624483A (zh) * 2019-11-11 2019-12-31 清华大学 合成气一步法制芳烃的多级流化床反应器及反应循环系统

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108794294B (zh) 2017-04-27 2020-12-11 中国科学院大连化学物理研究所 流化床气体分布器、应用其的反应器及生产对二甲苯联产低碳烯烃的方法
CN108786669B (zh) 2017-04-27 2021-01-12 中国科学院大连化学物理研究所 流化床气体分布器、应用其的反应器及生产对二甲苯联产低碳烯烃的方法
US11858874B2 (en) 2020-12-21 2024-01-02 Lg Chem, Ltd. Method for preparing alpha-methylstyrene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894183B2 (en) * 2001-03-26 2005-05-17 Council Of Scientific And Industrial Research Method for gas—solid contacting in a bubbling fluidized bed reactor
CN101940898A (zh) * 2010-09-26 2011-01-12 河北科技大学 一种四氯化硅的回收利用方法及其装置
CN101954264A (zh) * 2010-04-20 2011-01-26 南通泰禾化工有限公司 合成间苯二甲腈的新型流化床反应器
WO2015094697A1 (fr) * 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Conversion de méthanol en oléfines et en para-xylène
CN106588527A (zh) * 2015-10-15 2017-04-26 中国石油化工股份有限公司 生产芳烃和低碳烯烃的再生反应系统及反应方法

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2539415A (en) * 1947-03-14 1951-01-30 Hydrocarbon Research Inc Process and apparatus for the synthesis of hydrocarbons
US2456035A (en) * 1948-01-02 1948-12-14 Phillips Petroleum Co Treatment of fluids with comminuted solids
US2768127A (en) * 1951-05-17 1956-10-23 Exxon Research Engineering Co Improved residual oil conversion process for the production of chemicals
US2893849A (en) 1956-05-01 1959-07-07 Standard Oil Co Fluidized solids contacting apparatus
US3298793A (en) * 1963-04-04 1967-01-17 Badger Co Fluid bed diffusion
GB1265770A (fr) 1969-07-01 1972-03-08
IL48991A (en) 1975-03-18 1978-04-30 Sun Ventures Inc Ammoxidation process
US4051069A (en) 1976-05-07 1977-09-27 Texaco Inc. Fluidized catalytic cracking regeneration process
GB1535797A (en) * 1976-05-07 1978-12-13 Texaco Development Corp Fluidized cracking catalyst regeneration process and apparatus
US4337120A (en) 1980-04-30 1982-06-29 Chevron Research Company Baffle system for staged turbulent bed
US4456504A (en) 1980-04-30 1984-06-26 Chevron Research Company Reactor vessel and process for thermally treating a granular solid
US4691031A (en) 1984-06-20 1987-09-01 Suciu George D Process for preventing backmixing in a fluidized bed vessel
JPH07101883B2 (ja) 1988-06-13 1995-11-01 富士電機株式会社 信号路二重化ループバックシステム
WO1997025307A1 (fr) 1994-07-08 1997-07-17 Asahi Kasei Kogyo Kabushiki Kaisha PROCEDE POUR LA PRODUCTION DE NITRILE α.β-INSATURE
US6642426B1 (en) 1998-10-05 2003-11-04 David L. Johnson Fluid-bed aromatics alkylation with staged injection of alkylating agents
DE19903335A1 (de) * 1999-01-28 2000-08-17 Vinnolit Monomer Gmbh & Co Kg Verfahren für die Herstellung von 1,2-Dichlorethan aus der Oxichlorierung
MXPA02005987A (es) 1999-12-17 2004-08-12 Dow Global Technologies Inc Deshidrogenacion de un compuesto aromatico de alquilo y regeneracion de catalizador en un reactor de lecho fluidizado.
US6743400B2 (en) * 2001-03-21 2004-06-01 The Boc Group, Inc. Sparger configuration for fluidized bed hydrocarbon partial oxidation reactors
CN1208433C (zh) 2003-09-02 2005-06-29 中国石油化工集团公司 流化催化裂化装置待生催化剂分配器
CN101239870B (zh) 2007-02-07 2011-08-17 中国石油化工股份有限公司 甲醇和乙醇转化制低碳烯烃的方法
CN101279873B (zh) 2007-04-04 2011-03-23 中国石油化工股份有限公司上海石油化工研究院 由甲醇或二甲醚制备低碳烯烃的方法
CN201384946Y (zh) * 2009-03-24 2010-01-20 山东东岳有机硅材料有限公司 一种流化床反应器的气体分布器
DE102009039920A1 (de) * 2009-09-03 2011-03-10 Karl-Heinz Tetzlaff Verfahren und Vorrichtung zur Nutzung von Sauerstoff bei der Dampfreformierung von Biomasse
CN101723702B (zh) * 2009-09-04 2012-02-22 铁生年 高温流化床反应用微孔陶瓷气体分布板的制备方法
CN102372585B (zh) 2010-08-23 2015-12-09 中国石油化工股份有限公司 芳烃烷基化制对二甲苯的流化床方法
CN102464557B (zh) * 2010-11-17 2014-03-26 中国石油化工股份有限公司 由含氧化合物和甲苯制备二甲苯的方法
CN102875318B (zh) 2011-07-12 2015-01-07 中国石油化工股份有限公司 生产对二甲苯的反应-再生装置
TWI495511B (zh) * 2011-07-27 2015-08-11 Exxonmobil Chem Patents Inc 具有分階擋板的流體床反應器
CN203379868U (zh) 2013-07-16 2014-01-08 中石化洛阳工程有限公司 一种用于浆态床反应器的气体分布器
JP6145348B2 (ja) 2013-07-30 2017-06-07 新日鉄住金エンジニアリング株式会社 炭化水素合成用の反応器
WO2015081494A1 (fr) * 2013-12-03 2015-06-11 中国科学院大连化学物理研究所 Dispositif de réaction pour préparer des oléfines légères à partir de méthanol et/ou d'éther diméthylique
CN104971667B (zh) * 2014-04-01 2017-05-24 清华大学 一种由甲缩醛和多聚甲醛制备聚甲氧基二甲醚的流化床装置及方法
CN104177210B (zh) 2014-07-30 2016-05-18 清华大学 醇醚类化合物联产烯烃与芳烃的方法
CN204447967U (zh) * 2014-10-31 2015-07-08 中国石油天然气股份有限公司 一种流化催化反应器
CN104549073B (zh) 2015-01-05 2017-01-04 中国石油大学(华东) 一种烷烃脱氢制烯烃循环流化床反应装置
CN108786669B (zh) * 2017-04-27 2021-01-12 中国科学院大连化学物理研究所 流化床气体分布器、应用其的反应器及生产对二甲苯联产低碳烯烃的方法
CN108794294B (zh) 2017-04-27 2020-12-11 中国科学院大连化学物理研究所 流化床气体分布器、应用其的反应器及生产对二甲苯联产低碳烯烃的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894183B2 (en) * 2001-03-26 2005-05-17 Council Of Scientific And Industrial Research Method for gas—solid contacting in a bubbling fluidized bed reactor
CN101954264A (zh) * 2010-04-20 2011-01-26 南通泰禾化工有限公司 合成间苯二甲腈的新型流化床反应器
CN101940898A (zh) * 2010-09-26 2011-01-12 河北科技大学 一种四氯化硅的回收利用方法及其装置
WO2015094697A1 (fr) * 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Conversion de méthanol en oléfines et en para-xylène
CN106588527A (zh) * 2015-10-15 2017-04-26 中国石油化工股份有限公司 生产芳烃和低碳烯烃的再生反应系统及反应方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3617177A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110624483A (zh) * 2019-11-11 2019-12-31 清华大学 合成气一步法制芳烃的多级流化床反应器及反应循环系统

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JP7035077B2 (ja) 2022-03-14
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